Substituted 3-carbalkoxy 4-alkylamino-azobenzene compound as disperse dyestuffs for synthetic fibers

ABSTRACT

Azo dyestuffs, insoluble in water, are represented by the formula: ##STR1## wherein A represents the residue of a diazotizable benzene component carrying at least two substituents or the residue of a diazotizable heterocyclic component, R represents alkyl, B represents an unsubstituted or substituted alkyl group, and X represents hydrogen, chlorine, bromine, acylamino, benzoylamino, alkoxycarbonylamino, phenoxycarbonylamino, alkylsulfonylamino or phenylsulfonylamino, the dyestuff molecule being free of groups causing water solubility by formation of ions. These dyestuffs can be used for dyeing of hydrophobic fibers, in particular polyester fibers. Affinity is excellent and there are obtained bright, full-bodied shades very fast to wet tests, sublimation, abrasion and light.

The present invention relates to azo dyestuffs that are insoluble in water, which dyestuffs are particularly advantageous for the dyeing of hydrophobic fibers.

The dyestuffs of this invention may be represented by the general formula: ##STR2## wherein A represents the residue of a diazotizable benzene component carrying at least two substituents or the residue of a heterocyclic diazotizable component which may or may not be substituted;

R represents alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl;

B represents either

a residue of the formula --(CH₂)_(n) --OR' wherein n is a whole number from 1 to 4, preferably 2, and R' represents hydrogen or acyl of 2 to 5 carbon atoms, benzoyl, carbalkoxy of 2 to 5 carbon atoms, carbophenoxy, alkyl sulfonyl of 1 to 4 carbon atoms or phenysulfonyl, of

alkyl containing 1 to 4 carbon atoms or substituted alkyl of 1 to 4 carbon atoms wherein the substituent is one or more halogen atoms or one cyano, nitro, phenyl, pyridyl, pyrrolidonyl, phenoxy, alkoxy of 1 to 4 carbon atoms, carbophenoxy, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, acyl of 2 to 5 carbon atoms or cyanalkoxy of 2 to 5 carbon atoms or also a carbalkoxy group of 2 to 5 carbon atoms which can itself be substituted by cyano, acyl of 2 to 5 carbon atoms, carbalkoxy of 2 to 5 carbon atoms or acyloxy of 2 to 5 carbon atoms; and

X represents hydrogen, bromine, chlorine, acylamino of 2 to 5 carbon atoms, benzoylamino, alkoxycarbonylamino of 2 to 5 carbon atoms, phenoxycarbonylamino, alkylsulfonylamino of 1 to 4 carbon atoms or phenylsulfonylamino,

the dyestuffs molecule being free of groups causing hydrosolubility (water solubility) by formation of ions.

As examples of substituents of residue A, when A is arylene there are chlorine, cyano, nitro, mesyl, carbomethoxy, carbethoxy, phenylazo groups; and when A is heterocyclic, the substituent may be nitro, acetyl, carbethoxy, methyl, phenyl and cyano groups.

As examples of B residues, there can be cited more particularly the groups β-hydroxyethyl, β-acetoxyethyl, β-propionyloxyethyl, β-butyryloxyethyl, β-methoxy-carbonyloxyethyl, β-ethoxycarbonyloxyethyl, β-benzoyloxyethyl, β-phenoxycarbonyloxyethyl, β-mesyloxyethyl, β-phenylsulfonyloxyethyl, β-cyanethyl, β-chlorethyl, 3,3,4,4,4-pentafluorobutyl, benzyl, β-phenethyl, β-(2- or 4-pyridyl) ethyl, β-(2-oxo3-pyrrolidinyl) ethyl, β-methoxy (or ethoxy) ethyl, β-phenoxyethyl, β-carbomethoxyethyl, β-carbethoxyethyl, β-nitroethyl, β,γ-dichloropropyl, β-mesylethyl, β-ethylsulfonylethyl, β-phenylsulfonylethyl, β-acetylethyl, β-(2-cyanoethoxy) ethyl, β-phenoxycarbonylethyl, β-acetonyloxycarbonylethyl, β-(2acetyl carbethoxy) ethyl.

The dyestuffs of formula (I) can be prepared by coupling of the diazo derivative of an A--NH₂ base with a coupler of the formula: ##STR3## B, R and X being as defined above.

As diazotizable A--NH₂ bases there can be mentioned more particularly those of the formulae: ##STR4## wherein U represents chlorine, bromine, cyano, nitro, carbalkoxy or alkylsulfonyl, V represents cyano, nitro, alkylsulfonyl or phenylazo and W represents hydrogen, chlorine, bromine, cyano or nitro.

As example of diazotizable bases of the type of formula (III), there can be cited the following amines: 2-chloro or 2- bromo 4-nitro aniline, 2-chloro or 2-bromo 4-mesyl aniline, 2,4-dicyano aniline, 2,4-dicyano 6-chloro (or-bromo) aniline, 4-amino 5-mesyl 3-chloro (or bromo) benzonitrile, 2,6-dichloro 4-nitro aniline, 2,6-dibromo 4-nitro aniline, 2-amino 3-chloro (or bromo) 5-mesyl benzonitrile, 2,4-dinitro aniline, 2,4,6-trinitro aniline, 2,4-dinitro 6-chloro (or bromo) aniline, 2-amino 3,5-dinitro benzonitrile, 2-carbomethoxy 4-nitro aniline, 2-carbomethoxy 4,6-dinitro aniline, 2-carbomethoxy 4-nitro 6-chloro (or bromo) aniline, 2-carbomethoxy 4-nitro 6-cyano aniline, 2-amino 5-nitro benzonitrile, 2-amino 3-chloro (or bromo) 5-nitro benzonitrile, 2,6-dicyano 4-nitro aniline, 2-amino 3-mesyl 5-nitro benzonitrile, 2-mesyl 4-nitro aniline, 2-mesyl 4-nitro 6-chloro (or bromo) aniline, 2,4-dinitro 6-mesyl aniline.

As A--NH₂ diazotizable bases there can also be mentioned amino-monoazo compounds of the type of formula (IIIa) such as: 4-amino 3-chloro azobenzene, 4-amino 3-bromo azobenzene, 4-amino 3-nitro azobenzene, 4-amino 3-cyano azobenzene, 4-amino 3,5-dichloro azobenzene, 4-amino 3,5-dibromo azobenzene, 4-amino 3,5-dicyano azobenzene.

The A--NH₂ diazotable base can also be a heterocyclic compound such as: 2-amino 5-nitro thiazole, 2-amino 5-cyano thiazole, 2-amino 5-mesyl thiazole, 2-amino 6-bromo benzothiazole, 2-amino 6-chloro benzothiazole, 2-amino 6-nitro benzothiazole, 2-amino 6-cyano benzothiazole, 2-amino 6-mesyl benzothiazole, 2-amino 6-carbethoxy benzothiazole, 2-amino 6-(β-acetoxy-carbethoxy) benzothiazole, 3-amino 5-nitro 2,1-benzisothiazole, 3-amino 5-chloro 2,1-benzisothiazole, 3-amino 5-bromo 2,1-benzisothiazole, 3-amino 5-carbethoxy 2,1-benzisothiazole, 3-amino 5-mesyl 2,1-benzisothiazole, 2-amino 5-phenyl 1,3,4-thiadiazole, 2-amino 5-mesyl 1,3,4-thiadiazole, 2-amino 5-nitro 1,3,4-thiadiazole, 5-amino 1,2,4-thiadiazole, 3-phenyl 5-amino 1,2,4-thiadiazole, 2-amino 3-nitro 5-acetyl thiophene, 2-amino 3-cyano 5-carbethoxy thiophene, 3-methyl 5 -amino isothiazole, 3-methyl 4-nitro 5-amino isothiazole.

Diazotation of the A--NH₂ bases can be performed by the usual processes, for example with a nitrosylsulfuric acid in concentrated sulfuric acid or in a mixture of sulfuric acid-acetic acid-propionic acid.

Some couplers of formula (II) are already known. In a general way, they can be prepared by reaction of an anthranilate represented by the formula: ##STR5## where R and X are defined above, with a halide of the formula: B--hal in the presence of a neutralizing agent, such as calcium carbonate, or with a derivative carrying an activated ethylene bond, in the presence of a catalyst, such as acetic acid, copper acetate and benzyltrimethylammonium hydroxide.

Coupling of the diazo derivatives of the A--NH₂ bases with couplers of formula (II) can be performed in a known way, for example, in an acid medium, optionally in the presence of catalysts or buffering agents, as for example, pyridine and sodium acetate, which have an effect on the speed of the coupling reaction.

The dyestuffs of formula (I), wherein B represents a --(CH₂)_(n) --O-acyl residue, can also be prepared by esterification of the corresponding dyestuffs of formula (I), wherein B represents a --(CH₂)_(n) --OH residue, by means of an acid anhydride or acid chloride.

The dyestuffs of the invention, alone or in mixtures, are very suitable for dyeing or printing of various articles, particularly fibers and fabrics with a base of diacetate or triacetate of cellulose and of polyamides, but especially of aromatic polyesters. Affinity is excellent; and there are obtained bright, full-bodied shades very fast to wet tests, sublimation, abrasion or friction and light.

The dyestuffs of this invention are also very suitable for the dyeing of texturized yarns having a polyester base. They can also be used for the techniques of transfer printing and the relatively great solubility of a good number of them in solvents make possible their use for continuous dyeing in a solvent medium.

For dyeing applications, it is advantageous that the dyestuffs of this invention be in a finely divided state. This is why the dyes according to the invention are preferably pre-dispersed with dispersing agents, such as soap, alkali residues of sulfite cellulose, the products resulting from the condensation of naphthalene-sulfonic acids with formaldehyde, in particular, dinaphythylmethane-disulfonates, the sulfonated esters of succinic acid, the products obtained by condensation of cresols with formaldehyde and naphthol sulfonic acids.

Dyeing of the polyester fibers can be performed by impregnation in the presence of a vehicle at temperatures going from 80° C. to 125° C. or without vehicles or carriers under pressure between about 100° C. and 140° C. They can also be sized or printed with aqueous dispersions of the dyestuffs, then the impregnation obtained can be fixed between 140° and 220° C., for example, with superheated steam, air or by contact with a heating surface. The temperature range between 180° C. and 200° C. is particularly favorable for this purpose.

Instead of impregnation, the dyes according to the invention can also be applied by printing. For this purpose, there can be used, for example, a printing dye which contains in addition auxiliary agents currently used in printing, as wetting and thickening agents, the dyestuffs finely dispersed possibly in mixture with a dye for cotton and in the presence of urea and/or an acid-binding agent.

Because of their good wool and cotton reserve, the dyes according to the invention are also suitable for dyeing mixed polyester-wool and polyester-cotton fabrics.

The following examples, wherein proportions are by weight, unless indicated otherwise, illustrate the present invention.

EXAMPLE 1

There is heated, with reflux, for 30 hours a mixture of 75 parts of methyl anthranilate, 75 parts of ethyl acrylate, and 15 parts of crystallizable acetic acid. By distillation, there are obtained 41 parts of methyl N-(2-carbethoxyethyl) anthranilate which boils at 180° C. under 5 torrs.

    ______________________________________                                         Analysis:         C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.13 H.sub.17 NO.sub.4                                                        62.15    6.77     5.57                                       Found             62.3     6.77     5.71                                       ______________________________________                                    

EXAMPLE 2

The procedure of example 1 is followed, but the methyl anthranilate is replaced by 82.5 parts of ethyl anthranilate. There are obtained 55 parts of ethyl N-(2-carbethoxy ethyl) anthranilate which boils at 177° C. under 2 torrs.

    ______________________________________                                         Analysis:         C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.14 H.sub.19 NO.sub.4                                                        63.39    7.16     5.28                                       Found             63.06    6.94     5.33                                       ______________________________________                                    

EXAMPLE 3

There is heated, with reflux, for 8 hours a mixture of 165 parts of ethyl anthranilate, 50 parts of acrylonitrile and 5 parts of copper acetate. The reaction mass is filtered and the filtrate is distilled. There are obtained 75 parts of ethyl N-(2-cyanoethyl) anthranilate which boils at 170° C. under 1.5 torr.

    ______________________________________                                         Analysis:         C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.12 H.sub.14 N.sub.2 O.sub.2                                                 66.05    6.42     12.84                                      Found             65.74    6.28     12.8                                       ______________________________________                                    

EXAMPLE 4

There is heated, with reflux, for 30 hours, a mixture of 165 parts of ethyl anthranilate, 330 parts of ethylene chlorhydrin, 200 parts of calcium carbonate and 200 parts of water. It is filtered hot, the sludges are washed with 300 parts of hot water, the organic layer is decanted and distilled. Thus, there are obtained 43 parts of ethyl N-(2-hydroxyethyl) anthranilate which boils at 190° C. under 4 torrs.

    ______________________________________                                         Analysis:         C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.11 H.sub.15 NO.sub.3                                                        63.15    7.17     6.69                                       Found             63.10    7.11     6.60                                       ______________________________________                                    

EXAMPLE 5

There is heated, with reflux, for 16 hours a mixture of 48 parts of methyl N-(2-hydroxyethyl) anthranilate, 50 parts of crystallizable acetic acid and 25 parts of acetic anhydride. There are collected by distillation 42 parts of methyl N-(2-acetoxyethyl) anthranilate which boils at 178° C. under 1 torr.

    ______________________________________                                         Analysis:         C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.12 H.sub.15 NO.sub.4                                                        60.75    6.32     5.90                                       Found             60.51    6.37     5.98                                       ______________________________________                                    

EXAMPLE 6

There are dissolved 8.4 parts of 2-amino 5-nitro benzonitrile in 50 parts of a 50/50 mixture of acetic acid and propionic acid. It is cooled to 0°-5° C., then at this temperature there is introduced a mixture of 3.5 parts of sodium nitrite and 16.5 parts of sulfuric acid at 66° Be. It is left, with stirring, for 2 hours at 0°-5° C. and the excess nitrous acid is destroyed by addition of 0.1 part of urea. In the solution thus obtained, is poured a mixture of 12.6 parts of methyl N-(2-acetoxyethyl) anthranilate and 20 parts of crystallizable acetic acid. While the mixture is kept at 0°-5° C., there are gradually introduced into the mixture 30 parts of ice water. The precipitate is filtered, it is taken up in 300 parts of water, left, with stirring, for an hour and filtered again. With the dye thus obtained, i.e. 2-cyano 4-nitro 3'-carbomethoxy 4'-(2-acetoxyethylamino) azobenzene, polyester fibers are dyed a very bright scarlet shade presenting excellent properties, in particular a remarkable fastness to light.

The following table sets forth other examples of dyes according to the invention obtained as in example 6 by coupling of the diazo derivative of the A--NH₂ base indicated in the second column with the coupler of formula (II) indicated in the third column.

    ______________________________________                                                                              Color                                                                          on                                             A--NH.sub.2                     poly-                                     Ex.  Base     Coupler of formula (II)                                                                               ester                                     ______________________________________                                          7   2-amino  ethyl N-(2-acetoxyethyl)anthranilate                                                                  scarlet                                        5-nitro                                                                        benzoni-                                                                       trile                                                                      8   2-amino  methyl N-(2-hydroxyethyl)anthranilate                                                                 red                                            5-nitro                                                                        benzoni-                                                                       trile                                                                      9   2-amino  ethyl N-(2-hydroxyethyl)anthranilate                                                                  "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     10   2-amino  methyl N-(2-propionyloxyethyl)                                        5-nitro  anthranilate           scarlet                                        benzoni-                                                                       trile                                                                     11   2-amino  methyl N-(2-butyryloxyethyl)                                          5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     12   2-amino  methyl N-(2-benzoyloxyethyl)                                          5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     13   2-amino  ethyl N-(2-benzolyloxyethyl)                                          5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     14   2-amino  methyl N-(2-methoxycarbonyloxyethyl)                                  5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     15   2-amino  ethyl N-(2-methoxycarbonyloxyethyl)                                   5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     16   2-amino  methyl N-(2-ethoxycarbonyloxyethyl)                                   5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     17   2-amino  ethyl N-(2-ethoxycarbonyloxyethyl)                                    5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     18   2-amino  methyl N-(2-phenoxycarbonyloxyethyl)                                                                  "                                              5-nitro  anthranilate                                                          benzoni-                                                                       trile                                                                     19   2-amino  ethyl N-(2-phenoxycarbonyloxyethyl)                                                                   "                                              5-nitro  anthranilate                                                          benzoni-                                                                       trile                                                                     20   2-amino  2-(2-carbomethoxy phenylamino)-ethyl                                                                  "                                              5-nitro                                                                        benzoni- methanesulfonate                                                      trile                                                                     21   2-amino  2-(2-carbethoxy phenylamino)-ethyl                                                                    "                                              5-nitro  methanesulfonate                                                      benzoni-                                                                       trile                                                                     22   2-amino  2-(2-carbomethoxy phenylamino)-ethyl                                                                  "                                              5-nitro  benzenesulfonate                                                      benzoni-                                                                       trile                                                                     23   2-amino  2-(2-carbethoxy phenylamino)-ethyl                                                                    "                                              5-nitro  benzenesulfonate                                                      benzoni-                                                                       trile                                                                     24   2-amino  methyl N-(2-cyanoethyl)anthranilate                                                                   yellow                                         5-nitro                         scarlet                                        benzoni-                                                                       trile                                                                     25   2-amino  ethyl N-(2-cyanoethyl)anthranilate                                                                    "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     26   2-amino  methyl N-(2-chloroethyl)anthranilate                                                                  scarlet                                        5-nitro                                                                        benzoni-                                                                       trile                                                                     27   2-amino  ethyl N-(2-chloroethyl)anthranilate                                                                   "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     28   2-amino  methyl N-(3,3,4,4,4-pentafluorobutyl)                                                                 yellow                                         5-nitro  anthranilate           scarlet                                        benzoni-                                                                       trile                                                                     29   2-amino  ethyl N-(3,3,4,4,4-pentafluorobutyl)                                                                  "                                              5-nitro  anthranilate                                                          benzoni-                                                                       trile                                                                     30   2-amino  methyl N-benzyl anthranilate                                                                          scarlet                                        5-nitro                                                                        benzoni-                                                                       trile                                                                     31   2-amino  ethyl N-benzyl anthranilate                                                                           "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     32   2-amino  methyl N-phenethyl anthranilate                                                                       "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     33   2-amino  ethyl N-phenethyl anthranilate                                                                        "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     34   2-amino  methyl N-β-(2-pyridyl)ethyl                                      5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     35   2-amino  ethyl N-β-(2-pyridyl)ethyl anthranilate                                                          "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     36   2-amino  methyl N-β-(4-pyridyl)ethyl                                                                      "                                              5-nitro  anthranilate                                                          benzoni-                                                                       trile                                                                     37   2-amino  ethyl N-β-(4-pyridyl)ethyl anthranilate                                                          "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     38   2-amino  3-[2-(2-carbomethoxy phenylamino)                                                                     "                                              5-nitro  ethyl] 2-pyrrolidinone                                                benzoni-                                                                       trile                                                                     39   2-amino  3-[2-(2-carbethoxy phenylamino)ethyl]                                                                 "                                              5-nitro  2-pyrrolidone                                                         benzoni-                                                                       trile                                                                     40   2-amino  methyl N(2-methoxyethyl)anthranilate                                                                  "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     41   2-amino  ethyl N-(2-ethoxyethyl)anthranilate                                                                   "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     42   2-amino  methyl N-(2-phenoxyethyl)anthranilate                                                                 "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     43   2-amino  ethyl N-(2-phenoxyethyl)anthranilate                                                                  "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     44   2-amino  methyl N-(2-carbethoxyethyl)                                          5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     45   2-amino  ethyl N-(2-carbethoxyethyl)                                           5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     46   2-amino  phenyl 3-(2-carbomethoxy phenylamino)                                                                 "                                              5-nitro  propionate                                                            benzoni-                                                                       trile                                                                     47   2-amino  phenyl 3-(2-carbethoxy phenylamino)                                                                   "                                              5-nitro  propionate                                                            benzoni-                                                                       trile                                                                     48   2-amino  methyl N-(2-acetonyloxycarbonyl ethyl)                                5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     49   2-amino  oxo-3-butyl 3-(2-carbomethoxy                                                                         "                                              5-nitro  phenylamino)                                                          benzoni- propionate                                                            trile                                                                     50   2-amino  methyl N-(2-acetylethyl)anthranilate                                                                  "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     51   2-amino  ethyl N-(2-acetylethyl) anthranilate                                                                  "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     52   2-amino  methyl N-(2-β-cyanoethoxyethyl)                                  5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     53   2-amino  ethyl N-(2-β-cyanoethoxyethyl)                                   5-nitro  anthranilate           "                                              benzoni-                                                                       trile                                                                     54   2,6-di-  methyl N-(2-acetoxyethyl)                                                                             yellow                                         chloro   anthranilate           brown                                          4-nitro                                                                        aniline                                                                   55   2,6-di-  methyl N-(2-carbethoxyethyl)                                                                          "                                              chloro   anthranilate                                                          4-nitro                                                                        aniline                                                                   56   2,6-di-  methyl N-(2-methoxycarbonyloxyethyl)                                                                  "                                              chloro   anthranilate                                                          4-nitro                                                                        aniline                                                                   57   2,6-di-  methyl N-(2-cyanoethyl)                                                                               yellow                                         chloro   anthranilate           brown                                          4-nitro                                                                        aniline                                                                   58   2,6-di-  methyl N-phenethyl anthranilate                                                                       yellow                                         chloro                          brown                                          4-nitro                                                                        aniline                                                                   59   2-chloro methyl N-(2-acetoxyethyl)                                                      anthranilate           orange                                         4-nitro                                                                        aniline                                                                   60   2,6-di-  methyl N-(2-acetoxyethyl)                                                                             yellow                                         bromo    anthranilate           brown                                          4-nitro                                                                        aniline                                                                   61   2-bromo  methyl N-(2-acetoxyethyl)                                                                             orange                                         4-nitro  anthranilate                                                          aniline                                                                   62   2-chloro methyl N-(2-acetoxyethyl)                                                                             "                                              4-mesyl  anthranilate                                                          aniline                                                                   63   2-bromo  methyl N-(2-acetoxyethyl)                                                                             "                                              4-mesyl  anthranilate                                                          aniline                                                                   64   2,4-di-  methyl N-(2-acetoxyethyl)                                                                             "                                              cyano    anthranilate                                                          aniline                                                                                                        yellow                                    65   2-chloro methyl N-(2-acetoxyethyl)                                                                             scarlet                                        4,6-di-  anthranilate                                                          cyano                                                                          aniline                                                                   66   2-bromo  methyl N-(2-acetoxyethyl)                                                                             yellow                                                  anthranilate           scarlet                                        4,6-di-                                                                        cyano                                                                          aniline                                                                   67   2-chloro methyl N-(2-carbethoxy ethyl)                                                                         red                                            4,6-di-  anthranilate                                                          nitro                                                                          aniline                                                                   68   2-chloro methyl N-(2-acetoxy ethyl)anthranilate                                                                "                                              4,6-di-                                                                        nitro                                                                          aniline                                                                   69   2-chloro methyl N-(2-methoxycarbonyloxy ethyl)                                                                 "                                              4,6-di-                                                                        nitro                                                                          aniline                                                                                 anthranilate                                                     70   2-bromo  methyl N-phenethyl anthranilate                                                                       "                                              4,6-di-                                                                        nitro                                                                          aniline                                                                   71   2-amino  methyl N-(2-acetoxy ethyl)                                                                            red                                            3-chloro anthranilate                                                          5-nitro                                                                        benzoni-                                                                       trile                                                                     72   2-amino  methyl N-(2-carbethoxy ethyl)                                         3-chloro anthranilate           "                                              5-nitro                                                                        benzoni-                                                                       trile                                                                     73   2-amino  methyl N-(2-methoxycarbonyloxy ethyl)                                                                 "                                              3-chloro                                                                       5-nitro  anthranilate                                                          benzoni-                                                                       trile                                                                     74   2-amino  methyl N-phenethyl anthranilate                                                                       "                                              3-bromo                                                                        5-nitro                                                                        benzoni-                                                                       trile                                                                     75   methyl   methyl N-(2-acetoxy ethyl)                                                                            red                                            2-amino  anthranilate           orange                                         5-nitro                                                                        benzoate                                                                  76   methyl   methyl N-(2-carbethoxy ethyl)                                         2-amino  anthranilate           "                                              5-nitro                                                                        benzoate                                                                  77   methyl   methyl N-(2-acetoxy ethyl)                                            2-amino  anthranilate           "                                              5-nitro                                                                        benzoate                                                                  78   2-mesyl  methyl N-(2-acetoxy ethyl)                                                                            scarlet                                                 anthranilate                                                          4-nitro                                                                        aniline                                                                   79   2-mesyl  methyl N-(2-carbethoxy ethyl)                                         4-nitro  anthranilate           "                                              aniline                                                                   80   2-mesyl  methyl N-(2-methoxycarbonyloxy ethyl)                                                                 "                                              4-nitro  anthranilate                                                          aniline                                                                   81   4-amino  methyl N-(2-acetoxy ethyl)                                                                            orange                                                  anthranilate                                                          3-chloro                                                                       azoben-                                                                        zene                                                                      82   4-amino  methyl N-(2-acetoxy ethyl)                                                                            yellow                                                  anthranilate           brown                                          3,5-di-                                                                        chloro                                                                         azoben-                                                                        zene                                                                      83   4-amino  methyl N-(2-carbethoxy ethyl)                                                                         "                                              3,5-di-                                                                        chloro   anthranilate                                                          azoben-                                                                        zene                                                                      84   4-amino  methyl N-(2-methoxycarbonyloxy ethyl)                                                                 "                                              3,5-di-  anthranilate                                                          chloro                                                                         azoben-                                                                        zene                                                                      85   2-amino  methyl N-(2-acetoxy ethyl)anthranilate                                                                red                                            5-nitro                                                                        thiazole                                                                  86   2-amino  methyl N-(2-carbethoxy ethyl)                                         5-nitro  anthranilate           "                                              thiazole                                                                  87   2-amino  methyl N-(2-methoxycarbonyloxy ethyl)                                                                 "                                              5-nitro                                                                        thiazole anthranilate                                                     88   2-amino  methyl N-(2-carbethoxy ethyl)                                                                         "                                                       anthranilate                                                          6-nitro                                                                        benzo-                                                                         thiazole                                                                  89   2-amino  methyl N-(2-acetoxy ethyl)anthranilate                                                                "                                              6-nitro                                                                        benzo-                                                                         thiazole                                                                  90   2-amino  methyl N-(2-methoxycarbonyloxy ethyl)                                                                 "                                              6-nitro                                                                        benzo-   anthranilate                                                          thiazole                                                                  91   2-amino  methyl N-(2-acetoxy ethyl)anthranilate                                                                scarlet                                        6-carbethoxy                                                                   benzo-                                                                         thiazole                                                                  92   3-amino  "                      violet                                         5-nitro                                                                        2,1-benzi-                                                                     sothiazole                                                                93   3-amino  methyl N-(2-carbethoxy ethyl)                                                                         "                                              5-nitro  anthranilate                                                          2,1-benzi-                                                                     sothiazole                                                                94   3-amino  methyl N-(2-methoxycarbonyloxy ethyl)                                                                 violet                                                  anthranilate           red                                            5-nitro                                                                        2,1-benzi-                                                                     sothiazole                                                                95   2-amino  methyl N-(2-acetoxy ethyl)                                                                            scarlet                                                 anthranilate                                                          5-phenyl                                                                       1,3,4-thia-                                                                    diazole                         "                                         96   5-amino  methyl N-(2-acetoxy ethyl)                                                     anthranilate                                                          3-phenyl                                                                       1,2,4-thia-                                                                    diazole                                                                   97   5-acetyl methyl N-(2-acetoxy ethyl)                                                                            violet                                         2-amino  anthranilate           red                                            3-nitro                                                                        thiophene                                                                 98   2-amino  methyl N-(2-acetoxy ethyl)                                                                            scarlet                                                 anthranilate                                                          5-carbethoxy                                                                   3-cyano                                                                        4-methyl                                                                       thiophene                                                                 99   2-amino  ethyl 3-(5-acetylamino red                                                     2-carbomethoxy                                                        5-nitro                                                                        benzoni- phenylamino) propionate                                               trile                                                                     100  2-amino  methyl N-[3-(2-carbethoxy ethylamino)                                                                 "                                              5-nitro                                                                        benzoni- 4-carbomethoxy phenyl] carbamate                                      trile                                                                     101  2-amino  ethyl 3-(2-carbomethoxy                                                                               "                                              5-nitro  5-methylsulfonyl-                                                     benzoni- amino- phenylamino)                                                   trile    propionate                                                       102  2-amino  ethyl 3-(5-benzoylamino                                                                               "                                              5-nitro  2-carbomethoxy                                                        benzoni- phenylamino propionate                                                trile                                                                     103  2-amino  2-(2-carbomethoxy      "                                                       5-chloro phenylamino)                                                 3-chloro ethanol                                                               5-nitro                                                                        benzoni-                                                                       trile                                                                     104  2,4,6-tri-                                                                              N-(2-carbomethoxy 5-chloro phenyl)                                                                    "                                              nitro                                                                          aniline  ethylamine                                                       105  2,6-di-  methyl N-(2-hydroxyethyl)anthranilate                                                                 yellow                                         chloro   brown                                                                 4-nitro                                                                        aniline                                                                        2-chloro-                                                                      4-nitro  N-(2-hydroxyethyl)                                               106  aniline  anthranilate           orange                                    ______________________________________                                    

EXAMPLE 107

A fabric of polyester (polyethylene glycol terephthalate) fibers is printed with a printing paste containing 20 parts of the dyestuff described in example 80, 150 parts of a sulfonated castor oil sodium salt, 600 parts of a thickener and 250 parts of water. After drying, the fabric is heat set for a minute at 200° C. then subjected to a reducing treatment. There is obtained a scarlet shade presenting general good fastnesses, in particular a remarkable light fastness.

EXAMPLE 108

There are ground 1 part of the dyestuff obtained according to example 6 with 2 parts of a 50% aqueous solution of sodium salt of 1,1'-dinaphthyl 2,2'-methane-disulfonic acid. This dyeing preparation is dried, then diluted with 40 parts of water and 2 parts of 40% acetic acid are added, then water is added to obtain a dye bath of 4000 parts.

In this bath, brought to 50° C., are introduced 100 parts of polyester fibers, in a period of a half hour the temperature is raised to 120°-125° C. and dyeing is performed at this temperature for an hour in a closed container. Careful rinsing is then performed. There is obtained an intense scarlet dyeing having a remarkable resistance to light and excellent general properties.

EXAMPLE 109

A fabric of poly-ethylene glycol terephthalate fibers is sized in a solution of 10 parts of the dyestuff of example 74 in 1000 parts by volume of trichlorethylene, the fabric is dried and heat set for one minute at 180° C. then subjected to a reducing treatment. A red shade with general good fastnesses is obtained.

Further modifications and variations will be apparent to those skilled in the art. 

What is claimed is:
 1. A dyestuff represented by the formula: ##STR6## U is chlorine, bromine, cyano, nitro, carbomethoxy, carbethoxy or mesyl, V is cyano, nitro or mesyl,W is hydrogen, chlorine, bromine, cyano or nitro, R is alkyl containing 1 to 4 carbon atoms, X is hydrogen, bromine, chlorine, acetylamino, benzoylamino, alkoxycarbonylamino containing 2 to 5 carbon atoms, phenoxycarbonylamino, alkylsulfonylamino containing 1 to 4 carbon atoms or phenylsulfonyamino, and B isβ-chlorethyl, β,γ-dichloropropyl,
 3. 3,4,4,4-pentafluorobutyl,alkyl containing 1 to 4 carbon atoms unsubstituted or mono-substituted by cyano, nitro, phenyl, phenoxy, alkoxy containing 1 to 4 carbon atoms, carbophenoxy, alkylsulfonyl containing 1 to 4 carbon atoms, phenylsulfonyl, acetyl, cyanalkoxy containing 2 to 5 carbon atoms or carbalkoxy containing 2 to 5 carbon atoms, said carbalkoxy being unsubstituted or mono-substituted by cyano, acetyl or carbalkoxy containing 2 to 5 carbon atoms, or --(CH₂)_(n) --OR' wherein n is a whole number from 1 to 4 and R' is hydrogen, acetyl, propionyl, butyryl, benzoyl, carbalkoxy containing 2 to 5 carbon atoms, carbophenoxy, alkylsulfonyl containing 1 to 4 carbon atoms or phenylsulphonyl.
 2. A mixture of dyestuffs according to claim
 1. 